CN112048157A - Preparation method of flame-retardant epoxy resin composite material - Google Patents
Preparation method of flame-retardant epoxy resin composite material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses a preparation method of a flame-retardant epoxy resin composite material, which comprises the following steps: synthesizing a phosphorus-nitrogen flame retardant PDA-DOPO; adding a phosphorus-nitrogen flame retardant and magnesium hydroxide into epoxy resin according to a proportion; adding a certain proportion of silicon dioxide and zinc borate, and curing at 180 ℃ to obtain the epoxy resin composite material with high flame retardance and smoke suppression performance. According to the technical scheme, the epoxy resin is modified by the phosphorus-nitrogen flame retardant, so that the flame retardant efficiency can be effectively improved, and a certain amount of silicon dioxide and zinc borate are added, so that the composite material has strong surface adsorption force and is rapidly carbonized during combustion, the residual carbon content of the system is increased, the flame retardant and smoke suppression performance of the system is improved, and the fire-proof grade reaches the V-0 grade of UL-94 through testing. In addition, the flame-retardant epoxy resin composite material disclosed by the invention overcomes the defect of poor polymerization processability and mechanical property caused by only adding the inorganic flame retardant by adding the inorganic-organic phosphorus-nitrogen flame retardant, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of preparation of flame-retardant epoxy resin, and particularly relates to a preparation method of a flame-retardant glowing resin composite material.
Background
Epoxy resins (EP) are broadly defined as high molecular oligomers containing two or more epoxy groups in the molecular structure, the main molecular chain of which may be aliphatic, aromatic or alicyclic. The simple epoxy resin can be in various forms such as liquid, viscous and solid. Generally, the thermosetting high molecular polymer does not have good mechanical properties, and the application value of the thermosetting high molecular polymer can be reflected only by the curing and crosslinking reaction of the thermosetting high molecular polymer and a substance containing active hydrogen to generate insoluble and infusible thermosetting high molecular polymer. The epoxy resin can be used as a base material with mechanical property and electrical insulation property, and is widely applied to the fields of electronic and electrical product manufacturing, engineering composite materials, civil construction materials and the like. However, epoxy resin is easily burnt in fire and belongs to flammable materials, so that it is important to improve the flame retardancy of epoxy resin.
The common method for improving the flame retardancy of epoxy resin is to introduce halogen, nitrogen, silicon, phosphorus and other elements into the system, wherein the introduction of halogen into the system has the best effect. However, in the process of reusing and recycling the halogen-based epoxy resin, a large amount of toxic fumes and corrosive gases polluting the environment are emitted, such as: hydrogen halide, dioxin, benzofuran and the like, which not only pollute the environment, but also damage human organs after being inhaled by human bodies. The flame retardant is a chemical auxiliary agent capable of endowing a polymer with a flame retardant function, and is generally applied to various fireproof materials. Generally, the flame retardant is divided into an organic flame retardant and an inorganic flame retardant, wherein the inorganic flame retardant is decomposed when being heated, absorbs a large amount of heat to lower the temperature of surrounding materials, emits non-combustible gas, prevents a polymer from contacting with oxygen, and inhibits the combustion of the polymer. The organic phosphorus-containing flame retardant mainly comprises phosphate ester and the like, most of the organic phosphorus-containing flame retardants have flame retardant effect on a condensed phase at present, and the flame retardant effect comprises the steps of catalyzing carbon formation by phosphoric acid, insulating heat and oxygen by a porous carbon layer, forming a sticky film to cover the carbon layer, inhibiting flame combustion and the like.
The inorganic flame retardant applied to the epoxy resin comprises hydroxide, organic silicon and the like, and the addition of the inorganic flame retardant such as the organic silicon can reduce the internal stress of the epoxy resin, increase the toughness and the heat resistance of the epoxy resin and improve the flame retardant property of the epoxy resin. However, when the inorganic flame retardant is added into the epoxy resin, the processability and mechanical properties of the polymer are reduced, and the application of the polymer is influenced, so that the inorganic flame retardant is required to be matched with other flame retardants for use, and the comprehensive performance of the epoxy resin is improved by utilizing a synergistic effect.
Disclosure of Invention
The invention aims to provide a preparation method of a flame-retardant epoxy resin composite material, which comprises the following steps:
s1: adding 0.06mol of p-hydroxybenzaldehyde and 100mL of absolute ethyl alcohol into a three-neck round-bottom flask, placing the flask in a reactor with a reflux and stirring heating device, refluxing for 4h at 80 ℃, then slowly adding 0.03mol of diethylenetriamine, refluxing for 4h, and vacuum drying for 8h at 60 ℃ to obtain the imine PDA.
S2: adding 0.04mol of imine PDA and 0.08mol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into a three-neck round-bottom flask, adding 120mL of absolute ethyl alcohol, stirring, carrying out reflux reaction at 90 ℃ for 24h, cooling, carrying out suction filtration washing, and carrying out vacuum drying at 60 ℃ for 8h to obtain the phosphorus-nitrogen flame retardant PDA-DOPO.
S3: adding epoxy resin, a phosphorus-nitrogen flame retardant PDA-DOPO and magnesium hydroxide into a three-neck round-bottom flask according to a molar ratio of 1: 1-1.5: 0.4-0.8, and then placing the round-bottom flask on a reactor with a reflux and stirring heating device to stir at room temperature.
S4: mixing silicon dioxide and zinc borate according to a mass ratio of 1: 2-3, adding the mixture into a three-neck round-bottom flask obtained in the step S3, and raising the temperature of a reactor to 130 ℃ for reaction for 3 hours.
S5: and (4) pouring the compound after the reaction in the step S4 into a preheated iron mold while the compound is hot, placing the compound in a drying oven for curing at 140 ℃ for 2h, then heating to 180 ℃ for curing for 2h, cooling by a program at a cooling rate of 1.5 ℃/min to prevent cracking after the curing is finished, and opening the mold to room temperature to obtain the epoxy resin composite material.
Preferably, in step S3, the molar ratio of the epoxy resin, the PDA-DOPO and the magnesium hydroxide is 1:1 to 1.3:0.4 to 0.6.
Preferably, the imine PDA has a structural formula:
preferably, the weight ratio of the silica to the epoxy resin is 1: 20-35.
Preferably, in step S4, the mass ratio of silica to zinc borate is 1:2 to 2.5.
Preferably, the epoxy resin is E51 epoxy resin.
The invention has the following beneficial effects:
(1) the invention adopts the phosphorus-nitrogen flame retardant modified epoxy resin, can effectively improve the flame retardant efficiency, and the composite material reaches the V-0 level of UL-94.
(2) The invention adopts inorganic-organic phosphorus nitrogen flame retardant, achieves good synergistic flame retardant effect, and overcomes the defects of polymerization processability and mechanical property caused by only adding inorganic flame retardant.
(3) The phosphorus-nitrogen flame retardant adopted by the invention has a synergistic flame retardant effect with an inorganic flame retardant magnesium hydroxide, the heat absorption capacity of the magnesium hydroxide is 1.7kJ/mol, the P-C bond energy in PDA-DOPO is 264kJ/mol, and the heat of the prepared epoxy condensate is firstly absorbed by the flame retardant in the heating process, so that the effective flame retardant is achieved.
(4) The magnesium hydroxide in the inorganic-organic phosphorus-nitrogen flame retardant can preferentially absorb heat, so that the phosphorus-nitrogen flame retardant is prevented from generating smoke due to excessive heat absorption in combustion.
(5) According to the epoxy resin composite material prepared by the invention, a certain amount of silicon dioxide and zinc borate are added, so that the surface adsorption force of the composite material is strong, and the composite material rapidly forms carbon during combustion, thereby increasing the residual carbon content of a system and improving the flame retardant and smoke suppression performances of the composite material.
Drawings
FIG. 1 is a TG spectrum of the material prepared in example 1;
FIG. 2 is the FT-IR spectrum of the material prepared in example 1;
FIG. 3 is a graph of the LOI profile of the material prepared in example 1;
FIG. 4 is a loss tangent tan spectrum of the material prepared in example 1;
FIG. 5 is a total heat release curve of the material prepared in example 1;
FIG. 6 is an optical photograph of the epoxy composite after cone calorimetry testing of the material prepared in example 1.
Detailed Description
The following examples are provided for the purpose of illustration, and the present invention is not limited to the following examples.
Example 1
The preparation method of the flame-retardant epoxy resin composite material specifically comprises the following steps:
s1: adding 0.06mol of p-hydroxybenzaldehyde and 100mL of absolute ethyl alcohol into a three-neck round-bottom flask, placing the flask in a reactor with a reflux and stirring heating device, refluxing for 4h at 80 ℃, then slowly adding 0.03mol of diethylenetriamine, refluxing for 4h, and vacuum drying for 8h at 60 ℃ to obtain the imine PDA.
S2: adding 0.04mol of imine PDA and 0.08mol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into a three-neck round-bottom flask, adding 120mL of absolute ethyl alcohol, stirring, carrying out reflux reaction at 90 ℃ for 24h, cooling, carrying out suction filtration washing, and carrying out vacuum drying at 60 ℃ for 8h to obtain the phosphorus-nitrogen flame retardant PDA-DOPO.
S3: e51 epoxy resin, the phosphorus nitrogen flame retardant PDA-DOPO and magnesium hydroxide were added in a molar ratio of 1:1:0.4 to a three-necked round bottom flask, which was then placed on a reactor with a refluxing, stirred heating device and stirred at room temperature.
S4: mixing silicon dioxide and zinc borate according to a mass ratio of 1:2, adding the mixture into a step S3 three-neck round-bottom flask, and then raising the temperature of a reactor to 130 ℃ for reaction for 3 hours, wherein the weight ratio of the silicon dioxide to the E51 epoxy resin is 1: 20.
S5: and (4) pouring the compound after the reaction in the step S4 into a preheated iron mold while the compound is hot, placing the compound in a drying oven for curing at 140 ℃ for 2h, then heating to 180 ℃ for curing for 2h, cooling by a program at a cooling rate of 1.5 ℃/min to prevent cracking after the curing is finished, and opening the mold to room temperature to obtain the epoxy resin composite material.
Example 2
The preparation method of the flame-retardant epoxy resin composite material specifically comprises the following steps:
s1: adding 0.06mol of p-hydroxybenzaldehyde and 100mL of absolute ethyl alcohol into a three-neck round-bottom flask, placing the flask in a reactor with a reflux and stirring heating device, refluxing for 4h at 80 ℃, then slowly adding 0.03mol of diethylenetriamine, refluxing for 4h, and vacuum drying for 8h at 60 ℃ to obtain the imine PDA.
S2: adding 0.04mol of imine PDA and 0.08mol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into a three-neck round-bottom flask, adding 120mL of absolute ethyl alcohol, stirring, carrying out reflux reaction at 90 ℃ for 24h, cooling, carrying out suction filtration washing, and carrying out vacuum drying at 60 ℃ for 8h to obtain the phosphorus-nitrogen flame retardant PDA-DOPO.
S3: e51 epoxy resin, the phosphorus nitrogen flame retardant PDA-DOPO and magnesium hydroxide were added in a molar ratio of 1:1.5:0.8 to a three-necked round bottom flask, which was then placed on a reactor with a refluxing, stirred heating device and stirred at room temperature.
S4: mixing silicon dioxide and zinc borate according to the mass ratio of 1:3, adding the mixture into a three-neck round-bottom flask obtained in the step S3, and then raising the temperature of a reactor to 130 ℃ for reaction for 3 hours, wherein the weight ratio of the silicon dioxide to the E51 epoxy resin is 1: 35.
S5: and (4) pouring the compound after the reaction in the step S4 into a preheated iron mold while the compound is hot, placing the compound in a drying oven for curing at 140 ℃ for 2h, then heating to 180 ℃ for curing for 2h, cooling by a program at a cooling rate of 1.5 ℃/min to prevent cracking after the curing is finished, and opening the mold to room temperature to obtain the epoxy resin composite material.
Example 3
The preparation method of the flame-retardant epoxy resin composite material specifically comprises the following steps:
s1: adding 0.06mol of p-hydroxybenzaldehyde and 100mL of absolute ethyl alcohol into a three-neck round-bottom flask, placing the flask in a reactor with a reflux and stirring heating device, refluxing for 4h at 80 ℃, then slowly adding 0.03mol of diethylenetriamine, refluxing for 4h, and vacuum drying for 8h at 60 ℃ to obtain the imine PDA.
S2: adding 0.04mol of imine PDA and 0.08mol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into a three-neck round-bottom flask, adding 120mL of absolute ethyl alcohol, stirring, carrying out reflux reaction at 90 ℃ for 24h, cooling, carrying out suction filtration washing, and carrying out vacuum drying at 60 ℃ for 8h to obtain the phosphorus-nitrogen flame retardant PDA-DOPO.
S3: e51 epoxy resin, the phosphorus nitrogen flame retardant PDA-DOPO and magnesium hydroxide were added in a molar ratio of 1:1.2:06 to a three-necked round bottom flask, which was then placed on a reactor with a refluxing, stirred heating device and stirred at room temperature.
S4: mixing silicon dioxide and zinc borate according to a mass ratio of 1: 2.3, adding into a step S3 three-neck round-bottom flask, and then raising the temperature of the reactor to 130 ℃ for reaction for 3 hours, wherein the weight ratio of the silicon dioxide to the E51 epoxy resin is 1: 25.
S5: and (4) pouring the compound after the reaction in the step S4 into a preheated iron mold while the compound is hot, placing the compound in a drying oven for curing at 140 ℃ for 2h, then heating to 180 ℃ for curing for 2h, cooling by a program at a cooling rate of 1.5 ℃/min to prevent cracking after the curing is finished, and opening the mold to room temperature to obtain the epoxy resin composite material.
Example 4
The preparation method of the flame-retardant epoxy resin composite material specifically comprises the following steps:
s1: adding 0.06mol of p-hydroxybenzaldehyde and 100mL of absolute ethyl alcohol into a three-neck round-bottom flask, placing the flask in a reactor with a reflux and stirring heating device, refluxing for 4h at 80 ℃, then slowly adding 0.03mol of diethylenetriamine, refluxing for 4h, and vacuum drying for 8h at 60 ℃ to obtain the imine PDA.
S2: adding 0.04mol of imine PDA and 0.08mol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into a three-neck round-bottom flask, adding 120mL of absolute ethyl alcohol, stirring, carrying out reflux reaction at 90 ℃ for 24h, cooling, carrying out suction filtration washing, and carrying out vacuum drying at 60 ℃ for 8h to obtain the phosphorus-nitrogen flame retardant PDA-DOPO.
S3: e51 epoxy resin, the phosphorus nitrogen flame retardant PDA-DOPO and magnesium hydroxide were added in a molar ratio of 1:1.3:0.6 to a three-necked round bottom flask, which was then placed on a reactor with a refluxing, stirred heating device and stirred at room temperature.
S4: mixing silicon dioxide and zinc borate according to a mass ratio of 1: 2.6, adding into a step S3 three-neck round-bottom flask, and then raising the temperature of the reactor to 130 ℃ for reaction for 3 hours, wherein the weight ratio of the silicon dioxide to the E51 epoxy resin is 1: 30.
S5: and (4) pouring the compound after the reaction in the step S4 into a preheated iron mold while the compound is hot, placing the compound in a drying oven for curing at 140 ℃ for 2h, then heating to 180 ℃ for curing for 2h, cooling by a program at a cooling rate of 1.5 ℃/min to prevent cracking after the curing is finished, and opening the mold to room temperature to obtain the epoxy resin composite material.
Example 5
The preparation method of the flame-retardant epoxy resin composite material specifically comprises the following steps:
s1: adding 0.06mol of p-hydroxybenzaldehyde and 100mL of absolute ethyl alcohol into a three-neck round-bottom flask, placing the flask in a reactor with a reflux and stirring heating device, refluxing for 4h at 80 ℃, then slowly adding 0.03mol of diethylenetriamine, refluxing for 4h, and vacuum drying for 8h at 60 ℃ to obtain the imine PDA.
S2: adding 0.04mol of imine PDA and 0.08mol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into a three-neck round-bottom flask, adding 120mL of absolute ethyl alcohol, stirring, carrying out reflux reaction at 90 ℃ for 24h, cooling, carrying out suction filtration washing, and carrying out vacuum drying at 60 ℃ for 8h to obtain the phosphorus-nitrogen flame retardant PDA-DOPO.
S3: e51 epoxy resin, the phosphorus nitrogen flame retardant PDA-DOPO and magnesium hydroxide were added in a molar ratio of 1:1.4:0.7 to a three-necked round bottom flask, which was then placed on a reactor with a refluxing, stirred heating device and stirred at room temperature.
S4: mixing silicon dioxide and zinc borate according to a mass ratio of 1: 2.5, adding into a step S3 three-neck round-bottom flask, and then raising the temperature of the reactor to 130 ℃ for reaction for 3 hours, wherein the weight ratio of the silicon dioxide to the E51 epoxy resin is 1: 27.
S5: and (4) pouring the compound after the reaction in the step S4 into a preheated iron mold while the compound is hot, placing the compound in a drying oven for curing at 140 ℃ for 2h, then heating to 180 ℃ for curing for 2h, cooling by a program at a cooling rate of 1.5 ℃/min to prevent cracking after the curing is finished, and opening the mold to room temperature to obtain the epoxy resin composite material.
Comparative example 1
The preparation method of the flame retardant material specifically comprises the following steps:
s1: e51 epoxy resin, 4-diaminodiphenyl sulfone (DDS) and magnesium hydroxide were added in a 1:1:0.4 molar ratio to a three-necked round bottom flask, which was then placed on a reactor with a refluxing, stirred heating device and stirred at room temperature.
S2: silica was added to the three-necked round-bottomed flask of step S3 in a proportion of 4% epoxy resin, and then the reactor temperature was raised to 130 ℃ for reaction for 3 hours.
S3: and (4) pouring the compound after the reaction in the step S4 into a preheated iron mold while the compound is hot, placing the compound in a drying oven for curing at 140 ℃ for 2h, then heating to 180 ℃ for curing for 2h, cooling by a program at a cooling rate of 1.5 ℃/min to prevent cracking after the curing is finished, and opening the mold to room temperature to obtain the epoxy resin composite material.
Performance test experiments: the epoxy resin composite materials prepared in the embodiment 1 and the comparative example 1 have flame retardant efficiency, the epoxy resin composite material prepared in the embodiment 1 reaches V-0 grade of UL-94, and the limit epoxy index LOI value is higher than 40, while the epoxy resin composite material prepared in the comparative example 1 reaches V-1 grade of UL-94, and the limit epoxy index LOI value is only 22, which shows that the epoxy resin composite material prepared by the preparation method has excellent flame retardant property.
Claims (7)
1. The preparation method of the flame-retardant epoxy resin composite material is characterized by comprising the following steps:
s1: adding 0.06mol of p-hydroxybenzaldehyde and 100mL of absolute ethyl alcohol into a three-neck round-bottom flask, placing the flask in a reactor with a reflux and stirring heating device, refluxing at 80 ℃, then slowly adding 0.03mol of diethylenetriamine, refluxing for 4h, and vacuum drying at 60 ℃ for 8h to obtain imine PDA;
s2: adding 0.04mol of imine PDA and 0.08mol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into a three-neck round-bottom flask, adding 120mL of absolute ethyl alcohol, stirring, carrying out reflux reaction at 90 ℃ for 24h, cooling, carrying out suction filtration washing, and carrying out vacuum drying at 60 ℃ for 8h to obtain a phosphorus-nitrogen flame retardant PDA-DOPO;
s3: adding epoxy resin, a phosphorus-nitrogen flame retardant PDA-DOPO and magnesium hydroxide into a three-neck round-bottom flask according to a molar ratio of 1: 1-1.5: 0.4-0.8, and then placing the round-bottom flask on a reactor with a reflux and stirring heating device to stir at room temperature;
s4: mixing silicon dioxide and zinc borate according to the mass ratio of 1: 2-3, adding the mixture into a three-neck round-bottom flask obtained in the step S3, and then raising the temperature of a reactor to 130 ℃ for reaction for 3 hours;
s5: and (4) pouring the compound after the reaction in the step S4 into a preheated iron mold while the compound is hot, placing the compound in a drying oven for curing at 140 ℃ for 2h, then heating to 180 ℃ for curing for 2h, cooling by a program at a cooling rate of 1.5 ℃/min to prevent cracking after the curing is finished, and opening the mold to room temperature to obtain the epoxy resin composite material.
2. The method of claim 1, wherein the epoxy resin is E51 epoxy resin.
3. The method for preparing flame-retardant epoxy resin composite material according to claim 1, wherein said imine PDA has a structural formula:
4. the preparation method of the flame-retardant epoxy resin composite material as claimed in claim 1, wherein the weight ratio of the silica to the epoxy resin is 1: 20-35.
5. The method for preparing a flame retardant epoxy resin composite material according to claim 1, wherein the molar ratio of the epoxy resin, the PDA-DOPO and the magnesium hydroxide in the step S3 is 1: 1-1.3: 0.4-0.6.
6. The method of claim 1, wherein the refluxing at 80 ℃ for 4 hours in step S1 is performed.
7. The preparation method of the flame-retardant epoxy resin composite material according to claim 1, wherein the mass ratio of the silicon dioxide to the zinc borate in the step S4 is 1: 2-2.5.
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| CN112759529A (en) * | 2020-12-31 | 2021-05-07 | 陕西科技大学 | Bis (2-p-hydroxybenzeneimine) amine and preparation method thereof |
| CN113248789A (en) * | 2021-07-09 | 2021-08-13 | 衡阳师范学院 | Inorganic-organic hybrid phosphorus-nitrogen-containing flame retardant, preparation method thereof and modified epoxy resin |
| CN115947953A (en) * | 2022-12-28 | 2023-04-11 | 中国林业科学研究院林产化学工业研究所 | Toughening type lignin flame retardant and preparation method and application thereof |
| CN116102955A (en) * | 2023-01-31 | 2023-05-12 | 上海正欧实业有限公司 | Flame-retardant epoxy floor coating and preparation method thereof |
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| 卢庆新: "磷氮协同阻燃环氧树脂的制备及性能研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
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| CN113248789A (en) * | 2021-07-09 | 2021-08-13 | 衡阳师范学院 | Inorganic-organic hybrid phosphorus-nitrogen-containing flame retardant, preparation method thereof and modified epoxy resin |
| CN113248789B (en) * | 2021-07-09 | 2022-03-11 | 衡阳师范学院 | Inorganic-organic hybrid phosphorus-nitrogen-containing flame retardant, preparation method thereof and modified epoxy resin |
| CN115947953A (en) * | 2022-12-28 | 2023-04-11 | 中国林业科学研究院林产化学工业研究所 | Toughening type lignin flame retardant and preparation method and application thereof |
| CN116102955A (en) * | 2023-01-31 | 2023-05-12 | 上海正欧实业有限公司 | Flame-retardant epoxy floor coating and preparation method thereof |
| CN116102955B (en) * | 2023-01-31 | 2023-10-20 | 上海正欧实业有限公司 | Flame-retardant epoxy floor coating and preparation method thereof |
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